WO2012028989A1 - Process for producing carbon-comprising composite - Google Patents

Process for producing carbon-comprising composite Download PDF

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Publication number
WO2012028989A1
WO2012028989A1 PCT/IB2011/053646 IB2011053646W WO2012028989A1 WO 2012028989 A1 WO2012028989 A1 WO 2012028989A1 IB 2011053646 W IB2011053646 W IB 2011053646W WO 2012028989 A1 WO2012028989 A1 WO 2012028989A1
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WIPO (PCT)
Prior art keywords
acid
process according
composite
sulfur
metal
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PCT/IB2011/053646
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English (en)
French (fr)
Inventor
Natalia Trukhan
Ulrich Müller
Emi Leung
Alexander Panchenko
Nicole Janssen
Original Assignee
Basf Se
Basf (China) Company Limited
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Application filed by Basf Se, Basf (China) Company Limited filed Critical Basf Se
Priority to JP2013526572A priority Critical patent/JP2013537877A/ja
Priority to RU2013114186/04A priority patent/RU2013114186A/ru
Priority to CN2011800514847A priority patent/CN103180282A/zh
Priority to KR1020137007878A priority patent/KR20130101038A/ko
Priority to AU2011298030A priority patent/AU2011298030A1/en
Priority to MX2013002219A priority patent/MX2013002219A/es
Priority to EP11821197.8A priority patent/EP2611766A4/en
Priority to CA2809928A priority patent/CA2809928A1/en
Priority to BR112013004984A priority patent/BR112013004984A2/pt
Publication of WO2012028989A1 publication Critical patent/WO2012028989A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00853—Uses not provided for elsewhere in C04B2111/00 in electrochemical cells or batteries, e.g. fuel cells
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Composites are materials which comprise two or more bonded materials. Their precise chemical composition is frequently unknown, so that they usually have to be characterized by the process for producing them and also the starting materials.
  • An example is a composite produced from a porous metal-organic framework made up of cobalt ions and a nitrogen-comprising ligand (1 ,3,5-triazine-2,4,6-triyltrisglycine, TTG).
  • This composite is produced by pyrolysis and, owing to its nitrogen content, has good separation properties for the separation of C0 2 /CH 4 (Y. Shen et al., Chem. Commun. 46 (2010), 1308-1310).
  • the object is achieved by a process for producing a carbon-comprising composite, which comprises the step (a) Pyrolysis of a porous metal-organic framework comprising at least one at least bidentate organic compound coordinated to at least one metal ion under a protective gas atmosphere, where the at least one at least bidentate organic compound is nitrogen-free.
  • the process of the invention can comprise a further step (b).
  • a further step (b) an at least partial removal of one or more metal components from the composite obtained in step (a) is carried out.
  • This metal component or these metal components result from the transformation of the at least one metal ion comprised in the porous metal-organic framework.
  • the process of the invention can comprise a step (c) in which the composite obtained from step (a) or (b) is impregnated with sulfur.
  • the pyrolysis can be carried out by processes known in the prior art.
  • the pyrolysis in step (a) is preferably carried out at a temperature of at least 500°C, preferably at least 600°C.
  • the pyrolysis is more preferably carried out in a temperature range from 600°C to 1000°C, even more preferably in the range from 600°C to 800°C.
  • Process step (a) is carried out under a protective gas atmosphere.
  • the protective gas atmosphere is preferably an atmosphere of nitrogen.
  • Other generally known protective gases such as noble gases are also possible.
  • MOFs metal-organic frameworks
  • the metal-organic frameworks according to the present invention comprise pores, in particular micropores and/or mesopores.
  • Micropores are defined as pores having a diameter of 2 nm or less and mesopores are defined by a diameter in the range from 2 to 50 nm, in each case, corresponding to the definition given in Pure & Applied Chem. 57 (1983), 603 - 619, in particular on page 606.
  • the presence of micropores and/or misopores can be checked by means of sorption measurements which determine the uptake capacity for nitrogen of the MOF at 77 kelvin in accordance with DIN 66131 and/or DIN 66134.
  • the specific surface area, calculated according to the Langmuir model (DIN 66131 , 66134) for an MOF in powder form is greater than 100 m 2 /g, more preferably above 300 m 2 /g, more preferably greater than 700 m 2 /g, even more preferably greater than 800 m 2 /g, even more preferably greater than 1000 m 2 /g and particularly preferably greater than 1200 m 2 /g.
  • the metal component in the framework according to the present invention is preferably selected from groups la, lla, Ilia, IVa to Villa and lb to Vlb. Particular preference is given to Mg, Ca, Sr, Ba, Sc, Y, Ln, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, TI, Si, Ge, Sn, Pb, As, Sb and Bi, where Ln denotes lanthanides.
  • Lanthanides are La, Ce, Pr, Nd, Pm, Sm, En, Gd, Tb, Dy, Ho, Er, Tm, Yb.
  • radical R is not present.
  • groups are, inter alia, CH(SH) 2 , -C(SH) 3 , -CH(OH) 2 , or -C(OH) 3 .
  • the organic compounds comprising the at least two functional groups are preferably derived from a saturated or unsaturated aliphatic compound or an aromatic compound or a both aliphatic and aromatic compound.
  • the aliphatic compound or the aliphatic part of the both aliphatic and aromatic compound can be linear and/or branched and/or cyclic, with a plurality of rings per compound also being possible.
  • the aliphatic compound or the aliphatic part of the both aliphatic and aromatic compound more preferably comprises from 1 to 15, more preferably from 1 to 14, more preferably from 1 to 13, more preferably from 1 to 12, more preferably from 1 to 1 1 1 and particularly preferably from 1 to 10, carbon atoms, for example 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Particular preference is given here to, inter alia, methane, adamantine, acetylene, ethylene or butadiene.
  • the aromatic compound or the aromatic part of the both aromatic and aliphatic compound can have one or more rings, for example two, three, four or five rings, with the rings being able to be present separately and/or with at least two rings being fused.
  • the aromatic compound or the aromatic part of the both aliphatic and aromatic compound particularly preferably has one, two or three rings, with one or two rings being particularly preferred.
  • Each ring of the compound mentioned can also independently comprise at least one heteroatom such as O, S, B, P, Si, Al, preferably N, O and/or S.
  • the aromatic compound or the aromatic part of the both aromatic and aliphatic compound more preferably comprises one or two C 6 rings, with the rings being present either separately or in a fused form. Particular mention may be made of benzene, naphthalene and/or biphenyl as aromatic compounds.
  • the at least bidentate organic compound is more preferably an aliphatic or aromatic, acyclic or cyclic hydrocarbon which has from 1 to 18, preferably from 1 to 10 and in particular 6, carbon atoms and additionally has exclusively 2, 3 or 4 carboxyl groups as functional groups.
  • the at least bidentate organic compound is derived from a dicarboxylic acid such as oxalic acid, succinic acid, tartaric acid, 1 ,4-butanedicarboxylic acid, 1 ,4- butenedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1 ,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1 ,8-heptadecanedicarboxylic acid, 1 ,9-hepta- decanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1 ,2-benzenedicarboxylic acid, 1 ,3-benzenedicarboxylic acid, 1 ,3-butadiene-1 ,4- dicarboxylic acid, 1 ,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, thiophen
  • the at least bidentate organic compound is even more preferably one of the dicarboxylic acids mentioned by way of example above as such.
  • the at least bidentate organic compound is even more preferably one of the tricarboxylic acids mentioned by way of example above as such.
  • Examples of an at least bidentate organic compound derived from a tetracarboxylic acid are 1 ,1 -dioxidoperylo[1 ,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylene- tetracarboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid or (perylene 1 ,12- sulfone)-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acids such as 1 ,2,3,4- butanetetracarboxylic acid or meso-1 ,2,3,4-butanetetracarboxylic acid, decane-2, 4,6,8- tetracarboxylic acid , 1 ,4,7,10,13,16-hexaoxacyclooctadecane-2,3, 1 1 , 12-tetracarboxylic acid, 1 ,2,4,5-benz
  • the at least bidentate organic compound is even more preferably one of the tetracarboxylic acids mentioned by way of example above as such.
  • Very particular preference is given to optionally at least monosubstituted aromatic dicarboxylic, tricarboxylic or tetracarboxylic acids having one, two, three, four or more rings with each of the rings being able to comprise at least one heteroatom and two or more rings being able to comprise identical or different heteroatoms.
  • Suitable heteroatoms are, for example, O, S, B, P, and preferred heteroatoms among these are S and/or O.
  • suitable substituents mention may be made of, inter alia, -OH, a nitro group, an alkyl or alkoxy group.
  • acetylenedicarboxylic acid ADC
  • camphordicarboxylic acid fumaric acid
  • succinic acid benzenedicarboxylic acids
  • phthalic acid isophthalic acid, terephthalic acid (BDC)
  • naphthalenedicarboxylic acids NDC
  • biphenyldicarboxylic acids such as 4,4'-biphenyldicarboxylic acid (BPDC)
  • benzenetricarboxylic acids such as 1 ,2,3-, 1 ,2,4-benzenetricarboxylic acid or 1 ,3,5- benzenetricarboxylic acid (BTC), benzenetetracarboxylic acid, adamantanetetracarboxylic acid (ATC), adamantanedibenzoate (ADB), benzenetribenzoate (BTB), methanetetrabenzoate (MTB), adamantanetetrabenzoate or di
  • the metal-organic framework can also comprise one or more monodentate ligands and/or one or more at least bidentate ligands which are not derived from a dicarboxylic, tricarboxylic or tetracarboxylic acid.
  • the metal-organic framework can also comprise one or more monodentate ligands.
  • Suitable solvents for preparing the metal-organic framework are, inter alia, ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethyl sulfoxide, water, hydrogen peroxide, methylamine, sodium hydroxide solution, N- methylpyrrolidone ether, acetonitrile, benzyl chloride, triethylamine, ethylene glycol and mixtures thereof.
  • Further metal ions, at least bidentate organic compounds and solvents for the preparation of MOF are described, inter alia in US-A 5,648,508 or DE-A 101 1 1 230.
  • the pore size of the metal-organic framework can be controlled by selection of the suitable ligand and/or the at least bidentate organic compound. In general, the larger the organic compound, the greater the pore size.
  • the pore size is preferably from 0.2 nm to 30 nm, particularly preferably in the range from 0.3 nm to 3 nm, based on the crystalline material.
  • metal-organic frameworks examples are given below.
  • the metal and the at least bidentate ligand, the solvent and the cell parameters are indicated. The latter were determined by X-ray diffraction.
  • metal-organic frameworks are MOF-69 to 80, MOF103 to 106, MOF-177, MOF- 235, MOF-236, MOF-501 , MOF-502, MOF-505, IRMOF-1 , IRMOF-61 , IRMOP-51 , MIL- 45, MIL-47, MIL-53, MIL-59, MIL-60, MIL-61 , MIL-63, MIL-68, MIL-85, which are described in the literature.
  • metal-organic frameworks are MIL-53, Zn-tBu-isophthalic acid, AI-BDC, MOF-5, MOF-177, MOF-505, IRMOF-8, IRMOF-1 1 , Cu-BTC, AI-NDC, AI-BTC, Cu-BTC, AI-NDC, Mg-NDC, Al-fumarate, MOF-74, Sc-terephthalate. Even greater preference is given to AI-BDC, Al-fumarate, AI-NDC, AI-BTC and Cu-BTC.
  • the nitrogen-free at least one at least bidentate organic compound is preferably derived from a dicarboxylic, tricarboxylic or tetracarboxylic acid.
  • the term “derived” means that the at least one at least bidentate organic compound is present in partially or fully deprotonated form, as far as the carboxy functions are concerned.
  • the term “derived” means that the at least one at least bidentate organic compound can have further substituents.
  • substituents such as hydroxyl, methoxy, halogen or methyl groups can be present in addition to the carboxylic acid function. It is preferred that no further substituent, or only F substituents, is/are present.
  • the term "derived" also means that the carboxylic acid function can be present as sulfur analogues.
  • step (b) an at least partial removal of one or more metal components is carried out. It is preferred that this or these comprise at least one metal oxide.
  • the at least partial removal is preferably carried out by washing out by means of an alkaline liquid.
  • an alkaline liquid is, for example, an aqueous NaOH solution.
  • alkali metal hydroxides are also suitable.
  • an acid treatment is also possible.
  • step (c) an impregnation of the composite obtained from step (a) or (b) is carried out. Impregnation with chemicals is known and can be carried out as in the impregnation of porous metal-organic frameworks. This is described, for example, in the international patent application PCT/EP2010/053530.
  • the impregnation is preferably effected by mixing and subsequent heating.
  • the impregnation is preferably carried out by mechanical mixing.
  • Sulfur can be introduced as a solid or from a suspension or solution, in particular an organic solution such as a toluene-comprising solution, in particular a toluene solution.
  • the present invention further provides for the use of a composite material according to the invention which can be obtained by a process according to the invention for absorption of at least one material for the purposes of storage, removal, controlled release, chemical reaction of the material or as support.
  • the composite of the invention is used for storage, this is preferably carried out in a temperature range from -200°C to +80°C. A temperature range of from -40°C to +80°C is more preferred.
  • gas and liquid will be used in the interests of simplicity, but gas mixtures and liquid mixtures or liquid solutions are also encompassed by the term “gas” or "liquid”.
  • Preferred gases are hydrogen, natural gas, town gas, hydrocarbons, in particular methane, ethane, ethyne, acetylene, propane, n-butane and also i-butane, carbon monoxide, carbon dioxide, nitrogen oxides, oxygen, sulfur oxides, halogens, halogenated hydrocarbons, NF 3 , SF 6 , ammonia, boranes, phosphanes, hydrogen sulfide, amines, formaldehyde, noble gases, in particular helium, neon, argon, krypton and xenon.
  • the gas is particularly preferably carbon dioxide which is separated off from a gas mixture comprising carbon dioxide.
  • the gas mixture preferably comprises carbon dioxide together with at least H 2 , CH 4 or carbon monoxide.
  • the gas mixture comprises carbon monoxide in addition to carbon dioxide.
  • Very particular preference is given to mixtures which comprise at least 10 and not more than 45% by volume of carbon dioxide and at least 30 and not more than 90% by volume of carbon monoxide.
  • a preferred embodiment is pressure swing adsorption using a plurality of parallel adsorber reactors, with the adsorbent charge consisting entirely or partly of the material according to the invention.
  • the adsorption phase for the C0 2 /CO separation preferably takes place at a C0 2 partial pressure of from 0.6 to 3 bar and a temperature of at least 20°C but not more than 70°C.
  • the total pressure in the adsorber reactor concerned is usually reduced to values in the range from 100 mbar to 1 bar.
  • the minimum pressure is more preferably 200 bar (absolute), in particular 300 bar (absolute).
  • the gas is particularly preferably hydrogen or methane.
  • the liquid can be acetone, acetonitrile, aniline, anisole, benzene, benzonitrile, bromobenzene, butanol, tert-butanol, quinoline, chlorobenzene, chloroform, cyclohexane, diethylene glycol, diethyl ether, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, dioxane, glacial acetic acid, acetic anhydride, ethyl acetate, ethanol, ethylene carbonate, ethylene dichloride, ethylene glycol, ethylene glycol dimethyl ether, formamide, hexane, isopropanol, methanol, methoxypropanol, 3-methyl-1 -butanol, methylene chloride, methyl ethyl ketone, N- methylformamide, N-methylpyrrolidone, nitrobenzene, nitromethane, piperidine, propan
  • the odorous substance is preferably a volatile organic or inorganic compound which comprises at least one of the elements nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine or iodine, or is an unsaturated or aromatic hydrocarbon or a saturated or unsaturated aldehyde or a ketone. More preferred elements are nitrogen, oxygen, phosphorus, sulfur, chlorine, bromine; particular preference is given to nitrogen, oxygen, phosphorus and sulfur.
  • the odorous substance is ammonia, hydrogen sulfide, sulfur oxides, nitrogen oxides, ozone, cyclic or acyclic amines, thiols, thioethers and also aldehydes, ketones, esters, ethers, acids or alcohols.
  • the odorous substances can also be fragrances which are used, for example, for producing perfumes.
  • fragrances or oils which liberate such fragrances mention may be made by way of example of: essential oils, basil oil, geranium oil, mint oil, cananga tree oil, cardamom oil, lavender oil, peppermint oil, nutmeg oil, chamomile oil, eucalyptus oil, rosemary oil, lemon oil, lime oil, orange oil, bergamot oil, muscat sage oil, coriander oil, cypress oil, 1 ,1 -dimethoxy-2-phenylethane, 2,4-dimethyl-4- phenyltetrahydrofuran, dimethyltetrahydrobenzaldehyde, 2,6-dimethyl-7-octen-2-ol, 1 ,2-diethoxy-3,7-dimethyl-2,6-octadiene, phenylacetaldehyde, rose oxide, ethyl-2- methylpent
  • a volatile odorous substance preferably has a boiling point or boiling point range of less than 300°C.
  • the odorous substance is more preferably a readily volatile compound or mixture.
  • the odorous substance particularly preferably has a boiling point or boiling range of less than 250°C, more preferably less than 230°C, particularly preferably less than 200°C.
  • the metal-organic framework of the invention can serve as support, in particular as support for a catalyst.
  • the sulfur-impregnated composites of the present invention are suitable as sulfur electrode.
  • the present invention therefore further provides a sulfur electrode comprising such a composite according to the invention.
  • the present invention further provides for the use of a sulfur electrode according to the invention in an Li-sulfur battery and also provides an Li-sulfur battery comprising such a sulfur electrode.
  • AI-MOF Al-terephthalic acid MOF: 1 100 m 2 /g determined by the Langmuir method
  • Example 2 NaOH washing of the pyrolyzed Al-terephthalate
  • Elemental analysis Al 0.1 % by weight; Na 0.61 % by weight
  • Example 3 Loading of the material from Example 1 with sulfur. 1 .0 g of material from Example 1 and 6 g of sulfur are homogeneously mixed and heated at 180°C in an open apparatus for 6 hours. This gives 5.3 g of a solid dark gray substance which was milled to a fine powder by means of a ball mill.
  • Example 4 Loading of the material from Example 2 with sulfur.
  • Example 5 Production of an electrochemical cell according to the invention (electrode)
  • the dispersion is applied by means of a doctor blade to Al foil and dried at 40°C under reduced pressure for 10 hours.
  • Example 6 Production of a benchmark electrochemical cell 3.310 g of sulfur, 2.39 g of Super P, 0.19 g of KS 6, 0.25 g of Celvol binder are mixed together. The mixture is dispersed in a solvent mixture of 65% of H 2 0, 30% of isopropanol, 5% of 1 -methoxy-2-propanol. The dispersion is stirred for 10 hours.
  • Example 7 Testing of the electrochemical cell according to the invention
  • An electrochemical cell is built.
  • Anode Li foil 50 ⁇ thick, separator Tonen 15 ⁇ thick, cathode with composite material as described above.
  • Electrolyte 8% by weight of LiTFSI (LiN(S0 2 CF 3 ) 2 ), 4% by weight of LiN0 3 , 44% by weight of dioxolane and 44% by weight of dimethoxyethane.
PCT/IB2011/053646 2010-09-01 2011-08-18 Process for producing carbon-comprising composite WO2012028989A1 (en)

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JP2013526572A JP2013537877A (ja) 2010-09-01 2011-08-18 炭素含有複合体の製造方法
RU2013114186/04A RU2013114186A (ru) 2010-09-01 2011-08-18 Способ производства углеродсодержащего композита
CN2011800514847A CN103180282A (zh) 2010-09-01 2011-08-18 制备含碳复合材料的方法
KR1020137007878A KR20130101038A (ko) 2010-09-01 2011-08-18 탄소-함유 복합체의 제조 방법
AU2011298030A AU2011298030A1 (en) 2010-09-01 2011-08-18 Process for producing carbon-comprising composite
MX2013002219A MX2013002219A (es) 2010-09-01 2011-08-18 Proceso para producir compuesto que comprende carbono.
EP11821197.8A EP2611766A4 (en) 2010-09-01 2011-08-18 METHOD FOR PRODUCING A CARBON-CONTAINING COMPOUND
CA2809928A CA2809928A1 (en) 2010-09-01 2011-08-18 Process for producing carbon-comprising composite
BR112013004984A BR112013004984A2 (pt) 2010-09-01 2011-08-18 processo para produzir um compósito compreendendo carbono, compósito, uso de um compósito, eletrodo de enxofre, e, uso de um eletrodo de enxofre

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WO2015171613A1 (en) * 2014-05-05 2015-11-12 Nivo Systems, Inc. Carbon-enriched open framework composites, methods for producing and using such composites
US9527751B2 (en) 2011-11-11 2016-12-27 Basf Se Organotemplate-free synthetic process for the production of a zeolitic material of the CHA-type structure
DE102015215088A1 (de) 2015-08-07 2017-02-09 Robert Bosch Gmbh MOF-Silicium-Kohlenstoff-Komposit-Anodenmaterial
CN113725434A (zh) * 2021-08-06 2021-11-30 九江学院 一种镍基金属有机框架衍生的复合电极材料及其制备方法

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CN103500819B (zh) * 2013-09-18 2015-11-18 中南大学 一种表面修饰多孔状碳结构的碳纤维/硫复合正极材料及其制备方法
EP3049185B1 (en) * 2013-09-23 2019-12-11 Basf Se Process for the recovery of components forming a metal-organic framework material
WO2015137272A1 (ja) * 2014-03-11 2015-09-17 国立大学法人京都大学 多孔性構造体およびその製造方法並びに複合金属ナノ粒子の製造方法
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CN108336308A (zh) * 2017-01-20 2018-07-27 华为技术有限公司 一种锂硫电池正极保护材料及其应用
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CN110678419B (zh) 2017-05-19 2022-03-29 沙特阿拉伯石油公司 过渡金属金刚烷盐和氧化物纳米复合材料的合成
US10875092B2 (en) 2017-05-19 2020-12-29 Saudi Arabian Oil Company Methods for preparing mixed-metal oxide diamondoid nanocomposites and catalytic systems including the nanocomposites
CN107768652A (zh) * 2017-10-25 2018-03-06 北京理工大学 一种基于中微双孔金属氧化物或尖晶石的锂硫电池正极材料及其制备方法
CN109888236B (zh) * 2019-03-07 2021-09-28 南京邮电大学 一种锂硫电池正极材料的制备方法
CN111302476B (zh) * 2020-02-27 2021-12-17 南京大学 一种可活化过硫酸盐的mof原位生长cnt的磁性材料的制备与应用
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Publication number Priority date Publication date Assignee Title
US9099744B2 (en) 2011-03-31 2015-08-04 Basf Se Particulate porous carbon material and use thereof in lithium cells
US9527751B2 (en) 2011-11-11 2016-12-27 Basf Se Organotemplate-free synthetic process for the production of a zeolitic material of the CHA-type structure
WO2015171613A1 (en) * 2014-05-05 2015-11-12 Nivo Systems, Inc. Carbon-enriched open framework composites, methods for producing and using such composites
DE102015215088A1 (de) 2015-08-07 2017-02-09 Robert Bosch Gmbh MOF-Silicium-Kohlenstoff-Komposit-Anodenmaterial
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CN113725434A (zh) * 2021-08-06 2021-11-30 九江学院 一种镍基金属有机框架衍生的复合电极材料及其制备方法
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RU2013114186A (ru) 2014-10-10
KR20130101038A (ko) 2013-09-12
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MX2013002219A (es) 2013-06-03

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